We describe the construction and discuss the performance of a novel combined ultrahigh vacuum (UHV)-electrochemistry set-up, allowing the controlled preparation and structural characterization of complex nanostructured electrode surfaces by high resolution scanning tunnelling microscopy (STM) under UHV conditions on the one hand and, after electrode transfer under clean conditions, electrochemical measurements under continuous, controlled electrolyte mass transport conditions on the other. Electrochemical measurements can be coupled with online product detection, either using an additional collector electrode or by differential electrochemical mass spectrometry (DEMS). The potential of the set-up will be illustrated in two electrocatalytic reactions on complex, but structurally well-defined bimetallic electrode surfaces, O₂ reduction on Pt_xAg_1−x/Pt(111) monolayer surface alloys and bulk CO oxidation on Pt monolayer island modified Ru(0001) electrodes. We will particularly demonstrate the importance of structural characterization after the electrochemical measurements for identifying structural modifications induced by the electrochemical environment and thus avoiding misleading conclusions about the structure–activity relationships.